CN101029120B - Melt-processable polyurethanes and process for their preparation - Google Patents
Melt-processable polyurethanes and process for their preparation Download PDFInfo
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- CN101029120B CN101029120B CN2007100850294A CN200710085029A CN101029120B CN 101029120 B CN101029120 B CN 101029120B CN 2007100850294 A CN2007100850294 A CN 2007100850294A CN 200710085029 A CN200710085029 A CN 200710085029A CN 101029120 B CN101029120 B CN 101029120B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Melt processable polyurethanes containing certain waxes are produced. These polyurethanes are used in the manufacture of films, coatings and injection molded articles.
Description
Background of invention
The present invention relates to contain the urethane of the melt-processable of some wax, its manufacture method and they are used to make the purposes of film, coating and injection molding product.
Polyurethane Thermoplastic Elastomer (TPUs) has important industrial value, because they show excellent mechanical property, and can carry out melt-processed with cheap expense.Their mechanical property can be changed significantly by using the different chemical component.At Kunststoffe 68 (1978), 819-825 page or leaf and Kautschuk, Gummi, Kunststoffe 35 (1982), can find the general introduction of various TPU, their performance and application in the 568-584 page or leaf.
TPUs is by linear polyvalent alcohol, and normally polyester polyol or polyether glycol, organic diisocyanate and short-chain diol (chain extension agent) make up and form.To form the reaction acceleration in order making, also can to add catalyzer.The mol ratio of component can change significantly, makes that the performance of product can be adjusted.Depend on the mol ratio of polyvalent alcohol (one or more), can obtain the product that Shore hardness changes significantly chain extension agent (one or more).The polyurethane elastomer of melt-processable can progressively synthesize (prepolymer method) or make by the reaction (single stage method) simultaneously of one step of all components.In prepolymer method, polyvalent alcohol and vulcabond form and contain the prepolymer of isocyanic ester, and react with chain extension agent in second step.Can be continuously or make TPUs off and on.Foremost industrial process is band processing method (belt process) and forcing machine method.
Except catalyzer, also can in the TPU component, add auxiliary agent and additive.For example in TPUs industry manufacturing processed and in the course of processing at them, multiple wax plays a significant role.Wax plays internal lubricant and the exterior lubricant effect that reduces friction, thereby has improved the flowing property of TPU.In addition, it should prevent that TPU is adhered on the material on every side (for example, mould), and should play the dispersion agent effect of other additive such as pigment and antitack agent (antiblocking agent) as releasing agent.
In the prior art, the example of useful wax has: fatty acid ester, for example stearate and montanate and their metallic soap also have fatty acid amide, for example stearylamide and oleylamide, perhaps polyethylene wax.Can be at H.Zweifel (ed.): Plastics AdditivesHandbook (plastics additive handbook), the 5th edition, Hanser Verlag, Munich 2001, find the summary of the wax that is used for thermoplastics among the pp.443 ff..
So far, have the good not amide waxe, particularly ethylenedistearamide of sticking effect, be actually used in TPUs.In addition, show good lubrication performance and the low montanic acid ester type waxes of volatility be applied (referring to, for example EP-A 308683; EP-A 670339; JP-A5163431).But amide waxe shortcoming is their migratory aptitude when being used for TPUs.Over time, this can cause, and occurring on the workpiece oozes (plate out), causes impression impaired, particularly uses at thin-walled, and during for example film was used, nonconforming change took place the performance that the result causes having the surface to rely on.Too low mist degree limit the quantity of (haze limits) limited the use of montanic acid ester type waxes.And even adopted higher concentration, their not sticking effect is not enough.
By the specific wax mixture (DE-A 19 649 290) that uses ester and acid amides combination (DE-A 19 607 870) and pass through to use lignite acid derivative and derivative of fatty acid, this respect has had improved possibility.Really demonstrate significantly lower surface deposits formation tendency though contained the TPUs of these waxes,, these waxes also move under some weather condition, and this is unacceptable.
The invention summary
Therefore the purpose of this invention is to provide a kind of TPU,, and show good release property and non-viscosity simultaneously no matter its weather condition how, all do not form any surface deposition.
Mix with special additive by TPUs of the present invention, might realize this goal, the application will describe these additives more comprehensively.
Detailed Description Of The Invention
The present invention relates to the urethane of melt-processable, it is from following component manufacturing:
A) one or more organic diisocyanates,
B) the hydroxy-end capped polyvalent alcohol of one or more linearities, its weight-average molecular weight is 500 to 5000,
C) molecular weight is 60 to 490 one or more glycol chain extender and optional diamine chain extender,
D) Ren Xuan catalyzer (one or more),
E) optional adjuvants and additive and
F) account for the mixture of following reaction product of 0.02 to 2 weight % of the gross weight of product
A) Alkylenediamine (one or more), preferred quadrol, with one or more linear fatty acids, preferred stearic acid and/or palmitinic acid or industrial stearic acid and
B) Alkylenediamine (one or more), preferred quadrol, with the 12-oxystearic acid,
And/or
C) Alkylenediamine (one or more), preferred quadrol, with 12-oxystearic acid and one or more linear fatty acids, preferred stearic acid and/or palmitinic acid or industrial stearic acid.
The consumption of these components makes A) in the NCO group to B) and C) in the mol ratio of isocyanate-reactive group be 0.9: 1 to 1.2: 1.
Mixture F) comprise Alkylenediamine and a) and b) and/or c) by following preferred ratio: 1-95 weight % (preferred 1-85 weight %, 5-75 weight % most preferably) than 1-95 weight % (preferred 1-85 weight %, 5-75 weight % most preferably) than the reaction product of 0-50 weight % (preferred 0-40 weight %), ratio is based on the gross weight of mixture F, and the summation of reaction product equals 100 weight %.
The industry stearic acid comprises palmitinic acid and 50 to the 80 weight % stearic acid of 20 to 50 weight %.
Comprise that suitable organic diisocyanate A) vulcabond of aliphatic series, cyclic aliphatic, heterocycle and aromatics for example is for example at Justus Liebigs Annalen der Chemie, 562, those organic diisocyanates of describing among the pp.75-136.
The particular instance of suitable diisocyanates comprises: aliphatic vulcabond, for example hexamethylene diisocyanate; Cycloaliphatic diisocyanates, isophorone diisocyanate, 1 for example, 4-cyclohexyl diisocyanate, 1-methyl-2,4-cyclohexyl diisocyanate and 1-methyl-2,6-cyclohexyl diisocyanate and corresponding mixture of isomers, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate and 2,2 '-dicyclohexyl methane diisocyanate and corresponding mixture of isomers; Aromatic diisocyanate, for example 2, the 4-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate and 2,2 '-'-diphenylmethane diisocyanate, 2,4 '-diphenylmethanediisocyanate and 4,4 '-mixture of diphenylmethanediisocyanate, the liquid 4 of urethane modification, 4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate, 4,4 '-two isocyanic acid diphenylethanes-(1,2) and l,5 naphthylene diisocyanate.Preferred 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate mixture of isomers, wherein 4,4 '-'-diphenylmethane diisocyanate content＞96 weight %, most preferably 4,4 '-'-diphenylmethane diisocyanate and 1,5-naphthylene vulcabond.These vulcabond can use separately, perhaps use with form of mixtures each other.They can also with to the polyisocyanates of 15 weight % (based on the total amount of vulcabond) nearly, for example tritane-4,4 ', 4 " triisocyanate or polyphenyl polymethylene polyisocyanates use together.
The hydroxy-end capped polyvalent alcohol that with molecular weight is 500 to 5000 linearity is as B component).As their result of manufacturing, they usually contain a spot of nonlinear compound.Therefore, often claim that also they are " polyvalent alcohol of substantial linear ".The glycol of preferred polyester, polyethers or polycarbonate or its mixture.
Suitable polyether glycol can be made by the starting molecule reaction of one or more alkylene oxides that have 2 to 4 carbon atoms in the alkylidene group and the active hydrogen atom that contains 2 be tied (bound).The example of suitable alkylene oxide is: oxyethane, 1,2 epoxy prapane, epoxy chloropropane, 1,2-butylene oxide ring and 2,3-butylene oxide ring.The mixture of optimization ethylene oxide, propylene oxide and 1,2 epoxy prapane and oxyethane.These alkylene oxides can use separately, replacedly can use one by one or use as mixture.Suitable starting molecule for example is: water; Amino alcohol is as N-alkyl diethanolamine, for example N methyldiethanol amine; And glycol, as ethylene glycol, 1, ammediol, 1,4-butyleneglycol and 1,6-hexylene glycol.Also can randomly use the mixture of starting molecule.Suitable polyether glycol also comprises: the polymerisate of the hydroxyl group of tetrahydrofuran (THF).Also can adopt the polyethers of trifunctional, its ratio is 0 to the 30 weight % that accounts for the polyethers of two functional groups, but consumption is no more than the amount of enough generation melt-processable products.The molecular weight of the polyether glycol of substantial linear is 500 to 5000.They not only can use separately but also can use with the form of each other mixture.
Suitable polyester glycol can be by for example 2 to 12 carbon atoms, the dicarboxylic acid of preferred 4 to 6 carbon atoms and polyvalent alcohol manufacturing.Suitable dicarboxylic acid for example is: aliphatic dicarboxylic acid, and as succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid and sebacic acid, and aromatic dicarboxylic acid, as phthalic acid, m-phthalic acid and terephthalic acid.Can use these dicarboxylic acid separately, perhaps use these dicarboxylic acid, for example adopt the form of succsinic acid, pentanedioic acid and hexanodioic acid mixture with mixture.In order to make polyester glycol, can advantageously use corresponding dicarboxylic acid derivatives, as the carboxylic acid diesters that contains 1 to 4 carbon atom in the alcohol groups, the carboxylic acid anhydride that replaces these dicarboxylic acid or carboxylic acid chloride.Examples of polyhydric alcohols is: 2 to 10, the glycol of preferred 2 to 6 carbon atoms is as ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol, 2,2-dimethyl-1, ammediol, 1, ammediol and dipropylene glycol.Depend on needed performance, can use these polyvalent alcohols separately, perhaps optionally use with the form of its mixture each other.The ester that carbonic acid and above-mentioned glycol form also is suitable, the glycol of 4 to 6 carbon atoms is particularly arranged, as 1,4-butyleneglycol or 1,6-hexylene glycol, hydroxycarboxylic acid be the condensation product of hydroxycaproic acid for example, with the polymeric reaction product of lactone, for example choose the polymeric reaction product of the caprolactone that replaces wantonly.The preferred polyester glycol is: polyethylene glycol adipate, poly-hexanodioic acid 1,4-butanediol ester, poly-adipate glycol 1,4-butanediol ester, poly-hexanodioic acid 1,6-hexylene glycol DOPCP, poly-hexanodioic acid 1,6-hexylene glycol 1,4-butanediol ester and polycaprolactone.The molecular weight of these polyester glycols is 500 to 5000 and can uses separately or use with the form of the thing that is mixed with each other.
Be that 60 to 490 glycol is as chain extension agent C with molecular weight), the aliphatic diol of preferred 2 to 14 carbon atoms, as ethylene glycol, 1,6-hexylene glycol, glycol ether, dipropylene glycol, and more preferably 1, the 4-butyleneglycol.But following also is suitable, the diester that the dibasic alcohol of terephthalic acid and 2 to 4 carbon atoms forms, for example diglycol terephthalate or terephthalic acid two-1,4-butanediol ester; The hydroxy alkylidene ether of quinhydrones, as 1, the bis-phenol of 4-two (hydroxyethyl) quinhydrones and ethoxylation.Chain extension agent C) also can contain diamines than small proportion.These diamines comprise: (ring) aliphatic diamine, for example isophorone diamine, quadrol, 1,2-propylene diamine, 1,3-propylene diamine, N-methyl isophthalic acid, 3-propylene diamine, N, N '-dimethyl-ethylenediamine, and aromatic diamine, as 2,4-tolylene diamine and 2,6-tolylene diamine, 3,5-diethyl-2,4-tolylene diamine and 3,5-diethyl-2,6-tolylene diamine and uncle position (primary) be single-, two, three-or tetraalkyl-replacement 4,4 '-diaminodiphenyl-methane.Can also use the mixture of above-mentioned chain extension agent.In addition, can add more a spot of trivalent alcohol.
In addition, conventional simple function group compound can also be used on a small quantity, for example as chain terminator or releasing agent.For example: alcohols, as octanol and Stearyl alcohol, perhaps amine is as butylamine and octadecane amine.
In order to make TPUs of the present invention, these components can optionally be reacted in the presence of catalyzer, auxiliary agent and additive, their amount makes the NCO group to the summation of NCO reactive group, particularly the equivalence ratio of the OH base of low molecular weight diols/trivalent alcohol and polyvalent alcohol is 0.9: 1.0 to 1.2: 1.0, preferred 0.95: 1.0 to 1.10: 1.0.
TPUs of the present invention contains 0.02 to 2 weight % of the gross weight that accounts for TPU, the mixture of the reaction product particularly preferred wax component of the conduct of preferred 0.05 to 1.2 weight % F), the mixture of this reaction product be quadrol and a) industrial stearic acid (containing the palmitinic acid of 20 to 50 weight % and the stearic acid of 50 to 80 weight %) and b) the 12-oxystearic acid be about .05 with mol ratio a: b: 0.95 to about 0.95: 0.05, be preferably the mixture of reaction product of reaction in about 0.25: 0.75 to about 0.75: 0.25.
Can according to the amidation method of routine (referring to, for example, Houben und Weyl, Methodender organischen Chemie, the 4th edition, Thieme Publ.1952,8, the 647-671 pages or leaves) carry out this reaction.Under this situation, sour a) and b) can be jointly and the reacting ethylenediamine of equimolar amount, perhaps reaction the and subsequently acid amides that generates being mixed separately.Depend on manufacture method, form the mixture of the following reaction product that contains various ratios:
C16-EDA-C16 ethylenebis palmitic amide
C16-EDA-C18 ethylidene palmityl stearylamide
C16-EDA-C18OH ethylidene palmityl hydroxyl stearylamide
The C18EDA-C18 ethylenebisstearamide
C18-EDA-C18OH ethylidene stearyl-hydroxyl stearylamide
C18OH-EDA-C18OH ethylenebis hydroxyl stearylamide
Be applicable to the catalyzer D that TPU makes) comprise any conventional tertiary amine well known by persons skilled in the art, for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '-lupetazin, 2-(dimethylamino oxyethyl group) ethanol, diazabicyclo-[2.2.2]-octane, organometallic compound, for example titanic acid ester, iron cpd, tin compound are (for example, oxalic acid tin, two stannous octoates, two lauric acid tin, the perhaps dialkyltin salts of aliphatic carboxylic acid is as dibutyltin diacetate, dibutyl tin dilaurate and similar catalyzer).Preferred catalyzer is an organometallic compound, particularly titanic acid ester, iron cpd and/or tin compound.
Except TPU component, wax and catalyzer, also can add other auxiliary agent and additive E).Be exemplified below: lubricant, fatty acid ester for example, their metallic soap, fatty acid amide and silicon resin compound; Antitack agent (antiblocking agent); Inhibitor; Anti-hydrolysis, fast light, heat-resisting and anti-discolouring stablizer; Fire retardant; Dyestuff; Pigment; Inorganic or organic filler; And toughener.The preferably fibrous strongthener of toughener, inorganic fibre for example, it is according to the prior art manufacturing, and can provide with sizing material (size).Can be for example at J.H.Saunders, K.C.Frisch: " High Polymers[superpolymer] ", the XVI volume, urethane, the 1st and 2 parts, Interscience Publishers publishes 1962 and 1964 respectively; R.
H.M ü ller (ed.): Taschenbuch der Kunststoff-Additive, the 3rd edition, Hanser Verlag, Munich 1989; With the further details that finds relevant above-mentioned auxiliary agent and additive among the DE-A 2901774.
Other additive that can incorporate TPU into is a thermoplastics, for example polycarbonate and acrylonitrile/butadiene/styrene terpolymer, particularly ABS.Can also use other elastomerics, for example rubber, ethylene/acetic acid vinyl ester copolymer, styrene/butadiene copolymers and other TPUs.The commercialization softening agent, for example phosphoric acid ester, phthalic ester, adipic acid ester, sebate and alkyl sulfonic ester also are suitable for being impregnated in.
The present invention also provides the manufacture method of TPUs of the present invention.TPUs of the present invention can make with so-called " extrusion molding " for example in multiple screw extruder continuously.To each component A of TPU), B) and metering C) can carry out i.e. situation in single stage method simultaneously; Perhaps order is carried out, and promptly uses the situation of prepolymer method.The prepolymer of can packing into off and on, perhaps in a section of forcing machine or separating, make continuously in the prepolymer unit, upstream.
Can be with wax F) continuous measurement adds in the TPU reaction (system) in the forcing machine, preferably joins in the first forcing machine axle sleeve.Measure solid-state aggregate or measure with liquid form in room temperature at 70 to 120 ℃.But, also wax can be metered in advance and make good and in forcing machine once more among the fused TPU, and make their mix (compound).In another kind of version, can be before reaction, preferred temperature is 70 to 120 ℃, wax is evenly sneaked in the polyol component, and be metered in other component with polyol component.
The TPU product that obtains in this method has favorable mechanical performance and elasticity.In addition, they also have excellent processing characteristics.
When being processed to form injection molding product, because of the easily demoulding, so the excellence of TPUs of the present invention not viscosity can become apparent.Low migratory aptitude means: changing significantly under the storage requirement situation, even after long storage, also do not oozing (plate out).
The melt of available TPUs of the present invention is made the very film and the sheet material of homogeneous.Because their low adhesion tendency, these films and sheet material have extraordinary not viscosity.Owing to do not move, so even after standing storage, impression and surface property can not weakened yet.
Also TPUs of the present invention can be used as coating.
Be described in more detail the present invention by following examples.
Embodiment 1 to 6
The TPU preparation
Poly-(1, the 4-tetramethylene adipate) (molecular weight about 2200): 100 weight parts
Butyleneglycol: 11 weight parts
Diphenylmethanediisocyanate (MDI liquid, 50 ℃): 42 weight parts
Titanium acetyl acetonate: 7.5ppm
TPU makes
A tubular mixing tank/forcing machine (ZSK 53 forcing machines, Werner/Pfleiderer) in, with the working method of the known prepolymer of describing among EP-A 571830 and the EP-A 571828, make TPU with continuous T PU reaction.The axle sleeve temperature of 13 axle sleeves (housings) is 100 ℃ to 220 ℃.The speed of screw rod is transferred to 290rpm.Total metering speed is 75kg/h.TPU is extruded into molten filament, cooling and granulation in water.
Make wax or the mixture that adds in (ZSK axle sleeve 1) according to table 1 and 2 continuously at above-mentioned TPU.
Embodiment 7
TPU makes
With poly-(1 of 180 ℃ of 100 weight part temperature, the 4-tetramethylene adipate) (molecular weight about 2200), wherein dissolved the mixture of wax, with 42 weight part temperature be 60 ℃ warm 4,4 '-'-diphenylmethane diisocyanate (MDI) packs in the reactor that is stirring, and reaction is up to based on polyvalent alcohol transformation efficiency＞90 mole %.
Then, under intense mixing, mix 1 of 11 weight parts, the 4-butyleneglycol, and after about 15 seconds, reaction mixture is come down in torrents on the metal sheet (sheet) of coating, 120 ℃ of annealing 30 minutes.Cutting cast-sheet (sheets) and granulation.
The manufacturing of film: embodiment 8 to 10
Single screw extrusion machine (30/25D Plasticorder PL 2000-6 single screw extrusion machine, Brabender) (metering rate is 3 kilograms/hour; 185-205 ℃) in make the fusion of TPU pellet, by the inflation film die head it is extruded and is tubular-film.
The manufacturing of injection-molded sheet material 1 to 7
In injection molding machine (D-60 injection molding machine, 32 screw rods, Mannesmann AG) (about 225 ℃ of melt temperature), make the fusion of TPU pellet, be configured as sheet material (40 ℃ of die temperatures, sheets of sizes: the 125x45x2 millimeter).
With the most important performance inventory of the TPU moulded parts made in this way in table 1 and table 2.
Table 1: injection-molded sheet material
*Comparison test
Wax 1=
3324 (ethylenebisstearamides)
Wax 2=
Paradigm Wax 77 (stearic acid stearylamide ethyl ester)
Wax 3=wax mixture contains 7% ethylenebis palmitic amide, 25% ethylidene palmityl stearylamide, 13% ethylidene palmityl hydroxyl stearylamide, 24% ethylenebisstearamide, 24% ethylidene stearyl-hydroxyl stearylamide and 7% ethylenebis hydroxyl stearylamide; According to of the present invention
1: 1 mixture of wax 4=ethylenebisstearamide and Licowachs OP (montanic acid butyl ester, partly-hydrolysed) with Ca
Table 2: film
*Relatively
The result clearly illustrates that, only when using wax mixture 3 when (according to of the present invention), just after room temperature and 60 ℃ and 80 ℃ of storages, substantially all do not find surface deposition.On injection molding product and film, all can be observed the premium properties of TPU of the present invention.
Though aforementioned part illustrates for example, the present invention has been described in detail in detail, but has should be appreciated that such details just for illustrative purposes, those skilled in the art can not deviate from the spirit and scope of the present invention and make a change therein, and these spirit and scope only may be subjected to the qualification of claims.
Claims (7)
1. the urethane of a melt-processable, it is from following component:
A) one or more organic diisocyanates,
B) the hydroxy-end capped polyvalent alcohol of one or more linearities, its weight-average molecular weight is 500 to 5000,
C) molecular weight is 60 to 490 one or more glycol chain extender and optional diamine chain extender,
In the presence of following material, make:
D) Ren Xuan catalyzer
Add
E) optional adjuvants and additive,
Its amount makes A) in the NCO group to B) and C) in the mol ratio of isocyanate-reactive group be 0.9: 1 to 1.2: 1,
0.02 to the 2 weight % that contains the gross weight of the urethane that accounts for melt-processable
F) mixture of Yi Xia reaction product:
A) Alkylenediamine and one or more linear fatty acids and
B) Alkylenediamine and 12-oxystearic acid
And/or
C) Alkylenediamine and 12-oxystearic acid and one or more linear fatty acids.
2. the urethane of the melt-processable of claim 1, wherein
Component A) be 4,4 '-diphenylmethanediisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, l,5 naphthylene diisocyanate or 4,4 '-dicyclohexyl vulcabond or its mixture,
B component) be a kind of polyester glycol, polyether glycol, polycarbonate diol or their mixture of linearity, and
Component C) is ethylene glycol, butyleneglycol, hexylene glycol, 1,4 two (beta-hydroxy ethyl) quinhydrones, 1,4-two (beta-hydroxy ethyl) dihydroxyphenyl propane or their mixture.
3. the method for continuous production of the urethane of the melt-processable of claim 1 is wherein with mixture F) metering is with component A), B), C) and the component D that chooses wantonly) and E) add in the forcing machine.
4. the method for claim 3 is wherein in advance with mixture F) sneak into polyvalent alcohol B) in, and with this mix products with component A), C) and optional component D) and E) be metered in the forcing machine.
5. the coating that contains the urethane of right requirement 1.
6. the film that contains the urethane of right requirement 1.
7. the injection molding product that contains the urethane of right requirement 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006009096A DE102006009096B4 (en) | 2006-02-28 | 2006-02-28 | Thermoplastically processable polyurethanes, process for their preparation and their use |
| DE102006009096.9 | 2006-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101029120A CN101029120A (en) | 2007-09-05 |
| CN101029120B true CN101029120B (en) | 2011-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100850294A Active CN101029120B (en) | 2006-02-28 | 2007-02-28 | Melt-processable polyurethanes and process for their preparation |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20070203320A1 (en) |
| EP (1) | EP1826225B1 (en) |
| JP (1) | JP2007231274A (en) |
| KR (1) | KR20070089626A (en) |
| CN (1) | CN101029120B (en) |
| AT (1) | ATE471345T1 (en) |
| AU (1) | AU2007200539A1 (en) |
| BR (1) | BRPI0700473A (en) |
| CA (1) | CA2579544A1 (en) |
| DE (2) | DE102006009096B4 (en) |
| ES (1) | ES2345728T3 (en) |
| MX (1) | MX2007002234A (en) |
| SG (1) | SG135146A1 (en) |
| ZA (1) | ZA200701607B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006009097A1 (en) * | 2006-02-28 | 2007-08-30 | Clariant International Limited | Wax composition and its use |
| KR100901198B1 (en) * | 2007-06-19 | 2009-06-08 | 코오롱패션머티리얼 (주) | A method for preparation of an anti-phenolic yellowing polyurethane film |
| TW200942579A (en) * | 2008-02-26 | 2009-10-16 | Lubrizol Advanced Mat Inc | High moisture vapor transmissive polyurethanes |
| BRPI0913143A2 (en) * | 2008-09-10 | 2016-01-05 | Dow Global Technologies Llc | system and method of attaching a reactive adhesive to at least one substrate |
| BRPI0919216A2 (en) * | 2008-09-18 | 2015-12-08 | Basf Se | polyurethane and use of a polyurethane |
| EP2582757B1 (en) | 2010-06-15 | 2019-10-30 | Basf Se | Process for the production of blends of polylactides (pla) and thermoplastic polyurethanes (tpu) |
| US8633283B2 (en) | 2010-06-15 | 2014-01-21 | Basf Se | Process for producing blends made of polylactides (PLAS) and of thermoplastic polyurethanes (TPUS) |
| US8329854B2 (en) * | 2010-09-27 | 2012-12-11 | Xerox Corporation | Synthesis of tri-component resins |
| US20150183283A1 (en) | 2012-06-18 | 2015-07-02 | Basf Se | Valve for an inflatable hose section |
| US9957347B2 (en) | 2013-02-25 | 2018-05-01 | Basf Se | Reduced discoloration of thermoplastic polyurethanes based on polymer polyols via incorporation of aliphatic isocyanates |
| EP3016989B1 (en) | 2013-07-02 | 2023-08-09 | Basf Se | Polyurethane based on renewable resources |
| TW201609395A (en) * | 2014-07-11 | 2016-03-16 | 拜耳材料科學股份有限公司 | Water vapour-permeable composite components |
| EP3433294B1 (en) * | 2016-03-22 | 2021-09-01 | Lubrizol Advanced Materials, Inc. | Melt processable thermoplastic polyurethane-urea elastomers |
| ES2900361T3 (en) | 2017-07-14 | 2022-03-16 | Basf Se | Valve stem made of thermoplastic material |
| CN107987395A (en) * | 2017-12-29 | 2018-05-04 | 柴迪汉 | A kind of high intensity PP Wood-plastic materials and preparation method thereof |
| WO2023192919A1 (en) | 2022-03-30 | 2023-10-05 | Basf Se | Easy flow thermoplastic polyurethane (tpu) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257092A (en) * | 1998-12-16 | 2000-06-21 | 拜尔公司 | Aliphatic thermoplastic polyurethane, its preparation process and application |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635877A (en) * | 1969-07-07 | 1972-01-18 | Cpc International Inc | Use of heterocyclic acids in phenolic resins |
| JPH0826257B2 (en) * | 1987-03-24 | 1996-03-13 | 共栄社化学株式会社 | Anti-dripping agent for non-aqueous paint |
| US4877856A (en) * | 1987-08-31 | 1989-10-31 | The Bf Goodrich Company | Soft thermoplastic polyurethane for blown film application |
| DE3733752A1 (en) * | 1987-10-06 | 1989-04-20 | Bayer Ag | POLYETHER AND THEIR USE AS A MOLD RELEASE AGENT FOR PLASTICS |
| GB2244714B (en) * | 1990-05-31 | 1993-10-06 | Sanyo Chemical Ind Ltd | Foamed polyurethane-forming composition,foamed polyurethane and process for making the same |
| GB9014766D0 (en) * | 1990-07-03 | 1990-08-22 | Ici Plc | Fire retardant compositions |
| JP3121415B2 (en) | 1991-12-16 | 2000-12-25 | 株式会社クラレ | Thermoplastic polyurethane composition |
| DE4406948A1 (en) | 1994-03-03 | 1995-09-07 | Bayer Ag | Process for the production of thermoplastic polyurethane elastomers (TPU) |
| DE4428458A1 (en) * | 1994-08-11 | 1996-02-15 | Bayer Ag | Cycloaliphatic thermoplastic polyurethane elastomers |
| DE19514947C2 (en) * | 1995-04-24 | 1997-04-30 | Bayer Ag | Process for the preparation of TPU copolymer mixtures |
| DE19607870A1 (en) * | 1996-03-01 | 1997-09-04 | Bayer Ag | Wax containing thermoplastically processable polyurethanes |
| DE19649290A1 (en) * | 1996-11-28 | 1998-06-04 | Bayer Ag | Thermoplastic processable polyurethanes containing special wax mixtures |
| US6552153B1 (en) * | 1997-01-17 | 2003-04-22 | Bayer Aktiengesellschaft | Thermoplastic resins having incorporated mold release agents |
| US20020136848A1 (en) * | 1998-03-12 | 2002-09-26 | Fumio Yoshii | Lactone-containing resin composition, molded object thereof, and film |
| DE19940014A1 (en) * | 1998-12-16 | 2000-06-21 | Bayer Ag | Aliphatic thermoplastic polyurethanes, process for their preparation and their use |
| DE19924089C1 (en) * | 1999-05-26 | 2001-01-25 | Bayer Ag | Process for the continuous production of thermoplastically processable polyurethanes with improved softening behavior |
| DE10224847B4 (en) * | 2002-06-05 | 2006-04-13 | Clariant Gmbh | Reaction products of mixtures of long-chain fatty acids and aliphatic diamines and their use |
| DE102006009097A1 (en) * | 2006-02-28 | 2007-08-30 | Clariant International Limited | Wax composition and its use |
-
2006
- 2006-02-28 DE DE102006009096A patent/DE102006009096B4/en not_active Withdrawn - After Issue
-
2007
- 2007-02-07 AU AU2007200539A patent/AU2007200539A1/en not_active Abandoned
- 2007-02-21 EP EP07003527A patent/EP1826225B1/en active Active
- 2007-02-21 ES ES07003527T patent/ES2345728T3/en active Active
- 2007-02-21 DE DE502007004106T patent/DE502007004106D1/en active Active
- 2007-02-21 AT AT07003527T patent/ATE471345T1/en active
- 2007-02-22 US US11/709,411 patent/US20070203320A1/en not_active Abandoned
- 2007-02-23 MX MX2007002234A patent/MX2007002234A/en unknown
- 2007-02-23 ZA ZA200701607A patent/ZA200701607B/en unknown
- 2007-02-23 CA CA002579544A patent/CA2579544A1/en not_active Abandoned
- 2007-02-27 SG SG200701363-4A patent/SG135146A1/en unknown
- 2007-02-27 JP JP2007046988A patent/JP2007231274A/en active Pending
- 2007-02-27 KR KR1020070019645A patent/KR20070089626A/en not_active Application Discontinuation
- 2007-02-28 CN CN2007100850294A patent/CN101029120B/en active Active
- 2007-02-28 BR BRPI0700473-7A patent/BRPI0700473A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257092A (en) * | 1998-12-16 | 2000-06-21 | 拜尔公司 | Aliphatic thermoplastic polyurethane, its preparation process and application |
Non-Patent Citations (1)
| Title |
|---|
| JP昭63-235381A 1988.09.30 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2345728T3 (en) | 2010-09-30 |
| DE102006009096B4 (en) | 2009-06-10 |
| CA2579544A1 (en) | 2007-08-28 |
| CN101029120A (en) | 2007-09-05 |
| DE102006009096A1 (en) | 2007-09-06 |
| EP1826225A2 (en) | 2007-08-29 |
| DE502007004106D1 (en) | 2010-07-29 |
| MX2007002234A (en) | 2008-10-30 |
| US20070203320A1 (en) | 2007-08-30 |
| ATE471345T1 (en) | 2010-07-15 |
| EP1826225B1 (en) | 2010-06-16 |
| EP1826225A3 (en) | 2008-06-25 |
| KR20070089626A (en) | 2007-08-31 |
| SG135146A1 (en) | 2007-09-28 |
| JP2007231274A (en) | 2007-09-13 |
| ZA200701607B (en) | 2008-07-30 |
| BRPI0700473A (en) | 2007-11-06 |
| AU2007200539A1 (en) | 2007-09-13 |
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